Method of making halogenated aromatic hydrocarbon derivatives



Pu'nted Dec. 9, 1930 l vide improved'procedure capable of exce UNITED STATES PATENT] ornca EDGAR g. BB I'I'IOIAHD WEI-LIA! ROBE! MIDLAND, MICHIGAN, ABSIGNOBS so was now cannon. moment COMPANY, 01' MIDLAND, IIOHIGAN, CORPORATION 01' amen or name nno'emurnn non'n'c maocaano'x nmva'rrvas Io mung.

This invention relates to the pre aration of halogenated aromatic hydrocar ons; articularly of condensed nucleus type; and it is among the objects of the invention to pro- 1 ant yields. Other objects and advantages will ap ar as the description proceeds.

o the accomplishment of the foregoing and related ends, the invention, then, consists of the features hereinafter fully disclosed, and particularly ointed out in the claims, the following escription setting forth in detail a few of the various forms in which the principle of the invention may be applllied.

accordance with our invention, naphthalene is treated with a halogen while in a vehicle comprising a lower mo ecular weight compound containing a pluralit of atoms of carbon and of hydrogen that is, a hydrocarbon or halogenated hy rocarbon, as for instance benzene, toluene, xylenes, chlorobenzenes and the like, ordinary tem eratures being suitable. Parafiin hydrocar us may be used, but if contaminating olefins be present, there is a waste of the halogen.

We prefer to also include a catalyst, as iron, manganese, molybdenum, antimony, aluminum, FeCL, etc.

As an illustrative example: Into 150 parts by weight of naphthalene and 300 parts of benzene, in the presence of iron as catalyst,

chlorine is passed until about 0.8 mol. of

chlorine is absorbed. Hydrochloric acid re-.

maining in solution is removed by addition of soda ash and any excess of this together with resulting sodium chloride, is separated by filtration or decanting. On distillation of the filtrate about 95% of the benzene employed is removed, and about an 85% yield of alphachloronaphthalene on reacted naphthalene is obtained.

If the chlorination be continued until two mole. of chlorine are absorbed, a yield of dichloronaphthalenes is obtained. Instead of starting with the naphthalene as a batch charge, the naphthalene or the like may be supplied as the reaction proceeds.

n analogous manner, naphthalene may be Application me an, a, 1621. Serial in. 1mm.

treated with bromine, to the formation of brom-derivatives.

Other modes of applyin the principle of the invention may be emp 0 ed, chan e bein made as regards the detai disclose ,provi ed the steps stated in any of the following claims, or t e equivalent of such, be emplceyed.

e, therefore, particularly point out and distinctly claim as our invention 1. A rocess of makin mono and di halogen su stituted napht alene derivatives which comprises sub ecting naphthalene to the action of not more than the theoretically required proportion of a halogen in a liquid vehicle included within the group consisting of benzene, toluene, the xylenes and chlorobenzenes.

2. A recess of making mono and di halogensu stituted naphthalene derivatives which comprises Sub ecting naphthalene in the presence of a catalyst to the action of not more than the theoretically required proportion of a halogen in a liquid vehicle included within Y the group consisting of benzene, toluene, the xylenes, and chlorobenzenes.

3. A process of making mono and di chlorsubstituted naphthalene derivatives which comprises sub ecting naphthalene to the action of not more than the theoretically required proportion of chlorine in a liquid vehicle included within the oup consisting of benzene, toluene, the xy enes, and chlorobenzenes.

4. A process of making mono and di chlorsubstituted na hthalene derivatives which comprises sub ecting naphthalene to the action of not more than the theoretically required proportion of chlorine in a liquid vethalene which comprises reacting upon naphthelene in the presence of a catalyst with slightly less than one molecular equivalent of a halogen in a liquid vehicle included within the group consisting of .benzene,

toluene, the xylenes, and chlorobenzenes.

7. A process of making .mhloronephthalens which complrisesreacting upon naphthalene with sli tly less than one molecular 1 equivalent of c orine in a liquid vehicle included within the group consist' of hen-w zene, toluene, the xylenes, and c orobenmm. v

I 8. A process of making a-chloronephtha- 1 lens which comprises reacting upon naghthalens in the presence of a catalyst with s 'ghtly less than one molecular equivalent of chlorine in a liquid vehicle included within the up consisting of benzene, toluene, the xy enes, m and chlorobenzenes.

9. A process of making m-chloronaphthelens, which com rieesneacting upon us hthalene with sli tly less than one molec at equivalent of c orine in a vehicle of benzene.

.26 10. A process of making a-chloronephthalene, which comprises reacting upon nephthelene in the presence of it catalyst with slightly less than one molecular equivalent of chlorine in a vehicle of benzene.

.80 Signed by us this 23rd day of December,

1926. EDGAR C. BRITTON.

WILLIAM ROBERT REED. 

